Spectrally sensitized silver halide photographic emulsion

ABSTRACT

Photographic silver halide emulsions and color photographic light-sensitive materials containing same, which emulsions comprise at least one benzimidazolocarbocyanine dye combined with at least one pseudocyanine dye containing either a benzothiazole or benzoselenazole nucleus and hydroxy-substituted at the 5position thereof. The emulsions may optionally contain, in addition a compound containing a benzimidazole nucleus. The emulsions resulting from the above combination of ingredients are green-sensitive emulsions possessing a uniformly high spectrally sensitized sensitivity over a region from 480 to 580 Mu and are not affected adversely by the presence of a color coupler in the emulsion. Further, the above combination of additives do not produce color stain upon development.

United States Patent [72] lnventors Keisuke Shiba;

' Masanao Hinata; Akira Sato, all of Kanagawa, Japan [21] App1.No.856,487 [22] Filed Sept. 9, 1969 [45] Patented Nov. 2, 1971 [73]Assignee Fuji Photo Film Co., Ltd.

Kanagawa, Japan [32] Priority Sept. 9, 1968 [33] Japan [31 43/64854 [54]SPECTRALLY SENSITIZED SILVER HALIDE PHOTOGRAPHIC EMULSION 10 Claims, NoDrawings [52] US. Cl 96/124, 96/100, 260/240.6, 260/240.65, 260/2407,260/2408 [51] Int. Cl G03c 1/28, G03c 1/40 [50] Field of Search 96/1 04,106

[56] References Cited UNITED STATES PATENTS 2,052,754 9/1936 Dieterle eta1. 96/106 2,422,080 6/1947 Collins et a1. 96/104 2,973,264 2/1961 Nyset al 96/104 3,255,012 6/1966 Glockner et al 96/100 3,348,949 10/1967Bannert et a1. 96/104 3,463,640 8/1969 Fickcn et al. 96/104 PrimaryExaminerJohn T. Goolkasian Assistant Examiner-Robert A. Dawson Attorney-Sughrue, Rothwell, Mion, Zinn & Macpeak ABSTRACT: Photographic silverhalide emulsions and color photographic light-sensitive materialscontaining same, which emulsions comprise at least onebenzimidazolocarbocyanine dye combined with at least one pseudocyaninedye containing stabilizers present, the kind and properties Pat.

BACKGROUND OF TI-IE INVENTION Description of the Prior Art It is wellknown that spectral sensitizing is one of the techniques for producingsilver halide photographic-emulsions. The spectral sensitivity obtainedis largely influenced by the chemical structure of the sensitizing dyesused, the halogen composition of the silver halide contained in theemulsion, the crystalline system thereof, the extent of the chemicalsensitization, the method of the chemical sensitization, the pAg of theemulsion, the pH thereof, the kind of binder contained in the emulsion,the kind and properties of of antifoggants properties of the wettingagents emand properties of hardening agent present, the kinds andplayed, and the kinds present.

Moreover, such-additives frequently act to lower the spectrallysensitized sensitivity of the emulsion. In particular, in the case ofcolor photographic light-sensitive materials, the chemical structures ofthe sensitizing dyes and the manner of using them must be specificallyselected so thatthe adverse influences of the colored couplers containedin the emulsions on the spectrally sensitized sensitivity are reduced asmuch as possible.

Further, some sensitizing dyes are known to impart higher sensitivitywhen they are used together with other dyes or colorless aromaticcompounds having specific chemical structures, as compared with usingthese dyes individually. This is known as supersensitization.Combinations of compounds which provide supersensitization are requiredto be very rigidly selected. Thus, it is important to thespectral-sensitizing technique to find combinations of compounds whichwill coact to provide supersensitization.

Spectral sensitization for the green-sensitive region corresponding to aspectral region of high visual sensitivity is most important for thecolor reproduction of a color photographic light-sensitive material andthe quality of the color image formed thereon. In regard to the spectralsensitization of the green-sensitive region, there is described, e.g.,in US.

sensitizing action is only slightly obtained owing to the adverseinfluence of a color coupler present together with them. Moreover,although the method disclosed in the above U.S. patent results in asupersensitizing action, the supersensitization and the greensensitivity thus obtained are lower than those obtained by using acombination of, for example, a benzimidazolocarbocyanine dye and abenzoxazolo'carbocyanine dye (see Japanese Pat. Publication No. 4936/68One reason for the disadvantages of the method of the above U.S. patentis considered to be a harmful inhibiting action occurring during thedevelopment process. On the other hand, the method shown in theaforesaid Japanese Pat. Publication No. 4936/68 is accompanied by thedisadvantage that, although it may provide a high spectral sensitivityin the green region, contamination with dye remaining after thedevelopment procedure (hereinafter called "color stain) is large.Further, the latter method is accompanied by another disadvantage, inthat the sensitivity in the region from 500 to 530 m,u., which is aportion of the shorter wave length, green region, is relatively low. 7

No. 2,701,198, a method wherein a benzimidazolonecarbocyanine dye and apseudocyanine dye are used. However, wlieri this combination ofse'nsitizers is employed in emulsions of color photographiclight-sensitive materials, the spectral wherein Z, representsnonmetallic complete the benzimidazole nucleus; R represents an alkylfopropyl, a-sulfobutyl,

2 SUMMARY OF THE INVENTION Thus, an object of the present invention isto provide a green-sensitive photographic silver halide emulsion whichis not reduced in sensitivity when used in the presence ofa colorcoupler, which provides a uniformly high spectral sensitivity over theregion from 480 to 580 mp., and which further imparts no color stainafter the development procedure.

Another object of the present invention is to provide a colorphotographic light-sensitive material having, on a support, at least onelayer of the aforesaid photographic silver halide emulsion.

The inventors have found that of this invention can be attained byincorporating in a photographic silver halide emulsion at least one ofthe benzimidazolocarbocyanine dyes represented by the formula theabove-mentioned objects Ill Emmi a wherein 2;, represents nonmetallicatoms necessary to complete the quinoline nucleus; Y represents a sulfuratom or a selenium atomyR and R each represents an alkyl group or asubstituted alkyl group, at least one of said groups R, and R being asulfo-substituted alkyl group or a carboxy-substituted alkyl group; Arepresents a hydrogen atom, an alkyl group having one to four carbonatoms, or a' halogen atom; X represents an anion; and q is l or 2.

Moreover, as one embodiment of the present invention, it has been foundthat improved results can be obtained'by adding to the photographicsilver halide emulsion, together with the aforesaid dyes, at least oneof the compounds represented by the following formula atoms necessary togroup or a substituted alkyl group and 2, represents a phenyl group or asubstituted phenyl group.

DETAILED DESCRIPTION OF THE INVENTION As the sulfa-substituted alkylgroup represented by R, or R, in formula I, there may be exemplifiedB-sulfoethylfiy-suly-hydroxy-l-sulfopropyl, 2-(3-sulfoprop0xy)ethyl,2-[(3-sulfopropoxy)ethoxy]ethyl and the like. Further, as thecarboxy-substituted alkyl group represented by R or R there may beexemplified B-carboxyethyl, B-carboxypropyl, 2-(2-carboxyethoxy)ethyland the like. Moreover, as alkyl groups represented by R and R there maybe exemplified methyl, ethyl, n-propyl and the like. As thesubstituted-alkyl group, there may be exemplified, besides the aforesaidsulfo-substituted alkyl group and the carboxy-substituted alkyl group,B-hydroxyethyl, B-acetoxyethyl and the like.

Furthermore, as the alkyl group and the substituted alkyl grouprepresented by R, and R in formula 1, there may be exemplified methyl,ethyl, n-propyl, B-acetoxyethyl, and an alkyl group.

Z and Z of the formula represent the atoms necessary to complete thebenzimidazole nucleus, as mentioned before, and the benzimidazolenucleus may be halogen, cyano, trifluoromethyl, alkyl-aminosulfonyl, oracetyl-substituted.

The alkyl group or substituted alkyl group represented by R or R informula II are as set forth above in connection with R and R,,. At leastone of R and R is a substituted alkyl group having either a sulfo groupor a carboxyl group as set forth above in connection with R; and R,,. Z;in formula II represents the nonmetallic atoms necessary to complete aquinoline nucleus, as mentioned above, and the quinoline nucleus may besubstituted by a methyl group, an ethyl group, a hydroxyl group, analkoxyl group or a halogen atom.

X, and X, in general formulas l and II, respectively, are an anion, suchas, a bromine ion, an iodine ion, a thiocyanate ion, an alkylsulfateion, a perchlorate ion, and a p-toluenesulfonate ion. Also, the casewherein p is l and q is 1 in these formulas represents the formation ofan intramolecular salt.

R, in general formula III is the alkyl group or the substituted alkylgroup as set forth in connection with groups R; and R, in generalformula 1. Moreover, as the substituent for the substituted phenyl groupshown by group 2,, in general formula III, there may be illustrated analkyl group such as a methyl group, an ethyl group, or a propyl group;and alkoxyl group such as a methoxy group or an ethoxy group; and ahalogen atom such as a chlorine atom or bromine atom.

The feature of the sensitizing dye represented by general formula I isthat at least one of R and R is a sulfo-substituted alkyl group or acarboxy substituted alkyl group as mentioned above, which renders thedye reactive for supersensitization by the sensitizing dye representedby general formula ll as well as for supersensitization by the compoundrepresented by general formula III.

On the other hand, the feature of the sensitizing dye represented bygeneral formula ll is that the benzothiazole or the benzoselenazolenucleus has a hydroxyl group at the 5- position thereof and also atleast one of R and R is a sulfosubstituted alkyl group or a carboxylsubstituted alkyl group. Most preferably, R is a sulfo-substituted alkylgroup.

Sensitizing dyes wherein the benzothiazole or the benzoselenazolenucleus has a hydroxyl group at the 6-position have the drawback thatthe dye has high desensitizing properties and such dyes tend to form fogupon development. Also, sensitizing dyes having a hydroxyl group on thequinoline nucleus have the disadvantage that such dyes are weak insupersensitizing properties.

Accordingly, it is important that the sensitizing dye have a hydroxylgroup at the 5-position of the benzothiazole or benzoselenazole nucleus.

In general, when a pseudocyanine dye having no substituent on thenucleus is substituted by a sulfo-alkyl group at the 5- or 6-position ingeneral formula II, the dye provides hardly any spectral sensitivity.However, when a pseudocyanine dye having a hydroxyl group or a phenylgroup at the 5-position of the benzothiazole nucleus or benzoselenazolenucleus is substituted by a sulfo-alkyl group at R; or R in the generalformula, the spectral sensitivity obtained is markedly increased.

Furthermore, pseudocyanine dyes having a phenyl group at the 5-positionhave very weak supersensitizing action to the sensitizing dyerepresented by general formula I and form severe fog. On the other hand,pseudocyanine dyes having a hydroxyl group at the 5-position provide astrong supersensitizing action.

Since the pseudocyanine dye represented by general formula II and usedin the present invention has a sulfo-alkyl or a carboxy-alkyl group andalso has a hydroxyl group at the 5- position of the benzothiazole orbenzoselenazole nucleus, photographic light-sensitive material having aphotographic silver halide emulsion layer containing the dye gives lesscolor stain after development. Also, in the case of using the aforesaidpseudocyanine dye, the reduction in spectrally sensitized sensitivitycaused by the use of a color coupler is considerably less. However, theuse of said pseudocyanine dye is accompanied with the disadvantage thatthe dye is diffused into adjacent emulsion layers to spectrallysensitize said emulsion layers owing to the poor adsorption power of thedye to silver halide. On the other hand, when the pseudocyanine dyementioned above is used together with the sensitizing dye represented bygeneral formula I, the spectrally sensitized sensitivity obtained bysupersensitization is markedly increased, the harmful reduction ofsensitivity caused by the presence of a color coupler together with thepseudocyanine dye can be completely prevented, and also the formation ofcolor stain is reduced.

When the sensitizing dye represented by general formula ll is usedtogether with the sensitizing dye represented by general formula I, noharmful inhibiting action in development by the dyes occurs and, to thecontrary, the development tends to be promoted, each of which areparticular advantages of the present invention.

The sensitivity in the spectrally sensitive region of from 500 to 530 muobtained by the use of the combination of the sensitizing dyerepresented by general formula I and the sensitizing dye represented bygeneral formula ll is higher than the sensitivity in that regionobtained by the method disclosed in Japanese Pat. Publication No.4936/68 mentioned above but, strictly speaking, is still not as great asdesired. This difficulty can be overcome by further adding at least onecompound represented by general formula III.

The sensitizing dyes and, if necessary, the compound used in the presentinvention, may be dissolved in a water-miscible organic solvent such asmethanol, ethanol, alkalified ethanol, acidified methanol, acetone, orpyridine and they may be added to a photographic emulsion either as amixture or separately. The amount of the additive is varied according tothe kind of the silver halide emulsion to be employed but is preferablyfrom 1Xl0'6 mole to 1X 104 mole per g. of the silver halide emulsion.The order of addition of these additives and the proportions may bevaried according to the intended purpose.

In general, the ratio of the cyanine dye represented by general formulaII to the cyanine dye represented by the general formula I may be fromone-tenth to 10, the ratio of the cyanine dye represented by the generalformula Ill to the cyanine dye represented by the general formula I maybe from one-tenth to 10. As the photographic silver halide emulsion usedin the present invention, there may be mentioned silver chlorideemulsion, silver chlorobromide emulsion, silver bromide emulsion, silveriodobromide emulsion and the like. The photographic emulsion of thisinvention may further contain, aside from the sensitizing dyes of thepresent invention and, if necessary, the compound of general formulalll, such additives as a stabilizer, an antifoggant, a hardening agent,a wetting agent, a plasticizer, and the like. In particular, in the caseof preparing a coupler incorporated type of color photographiclight-sensitive material, a magenta coupler may be incorporated in thesilver halide emulsion containing the aforesaid additives.

The photographic silver halide emulsion of this invention, prepared bythe above-mentioned procedures, may be applied to a suitable supportsuch as a cellulose derivative film, a baryta-coated paper, a glassplate, a polyethylene terephthalate film and the like.

Examples of the sensitizing dyes and the compound of formula 111 used inthe present invention are shown below, although the invention is notlimited only to those shown.

sensitizing dyes represented by general formula I (IA) (lhHs (E2115C=CHCH=CH-C F 0 F N ((511928 OaNa MS a (1B) $3H5 (llzHs N N 01- -o1C=CH-CH=CHC I 01 t SO NHC;H

CrHs QSS 3 (IO) 532E: $2H5 O=CHOH=OHC C1 -Ol (CH2)4COOH (01104000151(ID) (12115 $H5 i v Cl -C1 C=CH--CH=OHC C1 -c1 N I (CH2CH2O)2(CH2)3SO3(C 2 2 )2( 2)aS 3 N(C2H6)a Sensitizing dyes represented by generalformula II:

IIA H3C S CH: \fi/ CH=C\ OH $2115 if] 93 3- (IIB) 01 s CH=C fi l I OHCH3 I? CHzC 00 HO 2 f CH=C m N/ OH CgHs 1? II D) i /se 011:0 i ID- 02 1?N lgHs IIE w a s l K \N CH= I 4 M a f MM Oa 2 i)a Compound representedby general formula III: 7

(IIIA) C2115 The sensitizing dyes represented by general formula I maybe prepared by the methods described in, for instance, thespecifications of U.S. Pat. No. 2,912,329 and Belgian Fat. Ni; 697,245.

Typical examples of preparing the sensitizing dyes represented bygeneral formula II are briefly shown below.

1. Preparation of dye (II A):

To a mixture of ml. of ethanol and 6 ml. of triethyl amine were added 1g. of l-ethyl-2-ethylmercapto-6-methylquinolinium p-toluenesulfonate andl g. of anhydro S-hydroxy-2,5-dimethyl-3-(y-sulfopropyl)benzothiazoliumhydroxide and the mixture was refluxed by heating for 1 hour to causethe reaction. The crystals thus precipitated were filtered, washed withwater, and recrystallized from a mixed solvent of methanol andchloroform to provide crystals of the dye (II A) having a melting pointhigher than 300 C. and a MaOH max.

of 506 my" Dyes (II B), (II C), (II D), and (ll E) can be also preparedby the above method.

2. the compounds represented by general formula 111 can be prepared bythe following manner.

2. Preparation of compound (III A):

In 70 ml. of acetone was suspended 4.7 g. of2-(5-anilinovinyl)-5,6-dichloro-l,3-diethylbenzimidazolium iodide and tothe suspension was added dropwise a solution of 2 g. of sodium hydroxidein 25 ml. of water with stirring at room temperature. After 20 minutes,a large amount of water was added to the solution prepared. The crystalsthus precipitated were filtered, washed with water, and recrystallizedfrom ligroin to provide 1.2 g. of crystals ofcompound (III A) having amelting point of 151 C. and

MeOH max.

of 384 mu.

Other compounds, e.g., (Ill B) and (III C) can be prepared by the aboveprocedure.

The following examples further illustrate the present invention.

EXAMPLE i In abeaker was melted 100 g. of a conventionally preparedgelatino silver iodobrornide emulsion (Agl 6.0 mole percent) and, afteradding to the emulsion a methanol solution of the sensitizing dye ormethanol solutions of the sensitizing dyes,

drying to provide a green-sensitive photographic silver halide EXAMPLE2' In a beaker was melted 100 g. of a conventionally prepared gelatinosilver iodobromide emulsion (Agl 4.0 mole percent) and, after adding tothe emulsion a methanol solution of the light Sensitive material' 5sensitizin d e or methanol solutions of the sensitizin d es The film wascut into strips and the same strip was exposed g y g y o 1 shown intable 2, the system was st1rred for 15 m1nutes at 35 to yellow llghtthrough Fu 1 Filter 012 (a yellow filter made by FM Photo Film co usinan ti 3] Wed 6 d C. Then 20 ml. of a 5 percent alkalme solut1on of amagenta subbcted t M g g l g i z g coupler having the followingstructure was added to the emulo a w e 1 opmen an en lo sion withstirring and the system was neutralized by the addito provide a blackand white negative image.

non of c1tr1c ac1d. By measurlng the denslty of the black and wh1tenegative image thus obtained, the relative green sensitivity was thenob- 0 tained. CH & f

0n the other hand, an unexposed sample strip obtained as 1 2 above wassubjected to a spectral exposure by means of a l reflection type gratingspectroscope and then subjected to H O -C=N black and white development.By measuring the density of the image, a distribution curve of spectralsensitization was ob- A h d i ag nt wa added to the emulsion andthereafter tamed. the emulsion was immediately applied to a film supportfol- These results are shown in table 1 together with the sensitizlo edby drying to provide a green-sensitive color photoing dyes and theamounts thereof employed. The black and graphic light-sensitivematerial. white development was conducted for 10 minutes at 20 C. in Thelight-sensitive film was cut into strips and the sample the developerhaving the following composition. strip was subjected to a yellowexposure by means of a sensitometer. The sample thus exposed wassubjected to a color Black and white developer development for 10minutes at 20 C. in a color developer,

containing as a color developing agent at N,N'-diethylamin0-Nmemybpmminopheml Km 4 8. p-aminoaniline derivative, having thefollowing composition; m w odlum ilfifig ham H H '7 so a- Hydroquinone 5I- Color developer Sodium Carbon!" (m hy rm) 8-N,N-diethylamino-p-aminoanillne 2.0 5. Potassium bromide 5 g. (u-atePotassium thiocyannte l g. Sodium gulf": 2 8' F flfl iodide 1 801W) 5Sodium carbonate (monohydrate) 50.0 g. make L000 (PH 10120-1)hlydroxylemine hydrochloride [.5 g. Potassium bromide l.() g.

Water to make 1,000 ml. TABLE 1 (pH 10.11101 (B) (c) (D) (E) The samplewas then subjected to first fixing, bleaching and second fixing toprovide a magenta image. By measuring the 1. 40 density of the magentaimage using a green light, a relative Mole, 1 1111. 70 0.08 563 greensensitivity was obtained. The results are shown in table 2 1111. 79 0.10553 2' (llA) lxIO'J mole, 2 1111. 100 0.15 5558 T BLE 2 4 1111. 126 0.205512 21111. 41111. 159 015 550-560 (A) (B) (C) (D) (IB) 4x10" 11) 4x10"mole, 1 1111. 40 0.13 564 mole, 1 1111. 71 0.019 580 2 1111. 56 0.17 5642 1111. 100 0.10 585 41111. 48 0.19 565 41111. 110 0.12 5113 113 11111.(lIA) 1x10" 50 2 1111. 11c 1 10" mole, 4 ml. I52 0.22 560 mole. 2 ml.158 0.l2 578 2 1111. 4 1111. 152 0.22 550 2 1111. 4 1111. 195 0.13 57621111. Sml. 188 0.14 540-570 2 1111. 66 0.011 550 l 28 o N 57 4 1111. 710.13 562 mo e, I rn 8 l. 98 .I

21111. 20 0.16 570 m o a 562 4 1111. 14 0.16 571 21111. 1112 1x10" 1o 410 11a 1 10'= 2 ml. Ml 0.16 550470 mole. 2 ml. mole, 2 ml. 42 0,10 5 0 21111. 4 1111. I60 0.17 550470 2 1111. 4 1111. I66 0.11 550-5so 2 1111.80 0.13 570 2 1111. s 1111. 200 013 545-500 4 1111. 100 0.17 570 60 21111. 79 0.011 550 a 1111. 89 0.21 570 4 1111. 109 0.09 550 s 1111. 1290.10 550 (lD)4x10" (llA) 1x10" Note: A) In order, the kind of thesens1t1z1n d e re resented mole, 2 1111. mole, 2 1111. 200 0.22 550473 gY P by general formula I, the concentrauon of the dye, and the ad- 2 ml.(HA) 4 1111. 250 0.25 550 578 dition amount thereof; (B) In order, thekind ofthe sensitizing 2 $3? gas 223' dye represented by general formulaII, the concentration of 4 166 562 the dye, and the addition amountthereof; (C) Relative se s 1111. 1711 0.32 562 sitivity; (D) Fog; and(E) Maximum sensitized wave length in mp" From the above results, it wasclear that by the combination Note: (A), (B), (C), (D), and (F) have thesame meanings of the two kinds of the sensitizing dyes represented bygeneral as those in table 1. formulas I and II, respectively, a highsupersensitization was The above procedure was followed except for theaddition obtained without increasing the formation of fog to any harmofa compound represented by the general formula III. The

ful extent.

results are shown below:

TABLE 3 (A) (B) (D) (E) (F) (IB) 4X10- mole: (IIC) 1X10- mole:

2ml 4m1 200 0.16 562 2ml 4m1 (IIIA) 1X10- mole, 21111.. 235 0.15 560(HA) 1X10- rnole:

Note: (A) In order, the sensitizing dye represented by general formulaI, concentration of the dye, and addition amount thereof; (B) in order,the sensitizing dye represented by general formula II, the concentrationof the dye, and the addition amount thereof; (C) In order, the compoundrepresented by general formula III, the concentration of the dye, andthe addition amount thereof; (D) Relative sensitivity; (E) Fog; and (F)The maximum sensitization wave length in mp.

What is claimed is:

1. A photographic silver halide emulsion comprising at least one cyaninedye represented by general formula] wherein Z and Z are each nonmetallicatoms necessary to complete the benzimidazole nucleus; R and R are eachselected from the group consisting of an alkyl group, a substitutedalkyl group and an allyl group; R and R. are each selected from thegroup consisting of an alkyl group and a substituted alkyl group, atleast one of said groups R and R being eTtlTfi6ih the groupcoHsTst'iiig" '6? a sulTo-su'b'stimted alkyl group and acarboxy-substituted alkyl group; X, is an anion, and p is l or 2 and atleast one cyanine dye represented by general formula 11 Fri-2+ (X?) 1-1is wherein 2 represents nonmetallic atoms necessary to complete aquinoline nucleus; Y is selected from the group consisting of a sulfuratom and a selenium atom; R and R are each selected from the groupconsisting of an alkyl group and a substituted alkyl group, at least oneof said groups R, and R being selected from the group consisting of asulfo-substituted alkyl group and a carboxy-substituted alkyl group; Ais selected from the group consisting of a hydrogen atom, an alkyl grouphaving one to four carbon atoms and a halogen atom; X is an anion and qis 1 or 2.

. (IIIB) 1X10 mole, 21111.. 282 0.15 540-560 2. The photographic silverhalide emulsion of claim 1 wherein said benzimidazolenucleus in generalformula I is substituted by at least one member selected from the groupconsisting of a halogen atom, a cyano group, a trichloromethyl group, analkylaminosulfonyl group and an acetyl group.

3. The photographic silver halide emulsion of claim 1 wherein saidquinoline nucleus in general formula II is substituted by at least onemember selected from the group consisting of a methyl group, an ethylgroup, a hydroxyl group, an alkoxyl group and a halogen atom.

4. The photographic silver halide emulsion of claim 1 wherein saidsulfo-substituted alkyl group represented by R; or R in general formula]and R or R in general formula II is selected from the group consistingof a [3 -sulfoethyl group, a 'ysulfopropyl group, a 'y-sulfobutyl group,a o-sulfobutyl group, a 2-hydroxy-l-sulfopropyl group, a2-(3-sulfopropoxy)ethyl group, and a 2-[2-(3-sulfopropoxy)ethoxylethylgroup.

5. The photographic silver halide emulsion of claim 1 wherein saidcarboxy-substituted alkyl group represented by R or R in general formulaland R and R in general formula II is selected from the group consistingof a B-carboxyethyl group, an a-carboxypropyl group and a2-(2-carb0xy-ethoxy)ethyl group.

6. The photographic silver halide emulsion of claim 1 wherein saidsilver halide emulsion containing said cyanine dyes is a green-sensitivesilver halide emulsion containing a magenta coupler for colorphotographic light-sensitive materi- 7. A color photographiclight-sensitive material comprising a support and at least one layer ofa photographic silver halide emulsion as set forth in claim 1.

8. A photographic silver halide emulsion as set forth in claim 1 furthercomprising at least one compound represented by general formula III I h(III) wherein 2., represents nonmetallic atoms necessary to complete abenzimidazole nucleus; Z is selected from the group consisting of aphenyl group and a substituted phenyl group; and R is selected from thegroup consisting of an alkyl group and a substituted alkyl group.

9. The photographic silver halide emulsion of claim 8 wherein saidsilver halide emulsion is a green sensitive silver halide emulsioncontaining a magenta coupler for color photographic light-sensitivematerial.

10. A color photographic light-sensitive material comprising a supportand at least one layer ofa silver halide emulsion as set forth in claim8.

2. The photographic silver halide emulsion of claim 1 wherein saidbenzimidazolenucleus in general formula I is substituted by at least onemember selected from the group consisting of a halogen atom, a cyanogroup, a trichloromethyl group, an alkylaminosulfonyl group and anacetyl group.
 3. The photographic silver halide emulsion of claim 1wherein said quinoline nucleus in general formula II is substituted byat least one member selected from the group consisting of a methylgroup, an ethyl group, a hydroxyl group, an alkoxyl group and a halogenatom.
 4. The photographic silver halide emulsion of claim 1 wherein saidsulfo-substituted alkyl group represented by R3 or R4 in general formulaI and R5 or R6 in general formula II is selected from the groupconsisting of a Beta -sulfoethyl group, a gamma -sulfopropyl group, agamma -sulfobutyl group, a delta -sulfobutyl group, a2-hydroxy-1-sulfopropyl group, a 2-(3-sulfopropoxy)ethyl group, and a2-(2-(3-sulfopropoxy)ethoxy)ethyl group.
 5. The photographic silverhalide emulsion of claim 1 wherein said carboxy-substituted alkyl grouprepresented by R3 or R4 in general formula I and R5 and R6 in generalformula II is selected from the group consisting of a Beta -carboxyethylgroup, an Alpha -carboxypropyl group and a 2-(2-carboxy-ethoxy)ethylgroup.
 6. The photographic silver halide emulsion of claim 1 whereinsaid silver halide emulsion containing said cyanine dyes is agreen-sensitive silver halide emulsion containing a magenta coupler forcolor photographic light-sensitive material.
 7. A color photographiclight-sensitive material comprising a support and at least one layer ofa photographic silver halide emulsion as set forth in claim
 1. 8. Aphotographic silver halide emulsion as set forth in claim 1 furthercomprising at least one compound represented by general formula III 9.The photographic silver halide emulsion of claim 8 wherein said silverhalide emulsion is a green sensitive silver halide emulsion containing amagenta coupler for color photographic light-sensitive material.
 10. Acolor photographic light-sensitive material comprising a support and atleast one layer of a silver halide emulsion as set forth in claim 8.